The Bethe–Salpeter formalism with polarisable continuum embedding: reconciling linear-response and state-specific features†,Chemical Science

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The Bethe–Salpeter formalism with polarisable continuum embedding: reconciling linear-response and state-specific features†
Chemical Science ( IF 7.6 ) Pub Date : 2018-04-05 00:00:00 , DOI: 10.1039/c8sc00529j
Ivan Duchemin ₁ , Ciro A Guido _{2,

3} , Denis Jacquemin ₂ , Xavier Blase ₄

Affiliation

The Bethe–Salpeter equation (BSE) formalism has been recently shown to be a valuable alternative to time-dependent density functional theory (TD-DFT) with the same computing time scaling with system size. In particular, problematic transitions for TD-DFT such as charge-transfer, Rydberg and cyanine-like excitations were shown to be accurately described with BSE. We demonstrate here that combining the BSE formalism with the polarisable continuum model (PCM) allows us to include simultaneously linear-response and state-specific contributions to solvatochromism. This is confirmed by exploring transitions of various natures (local, charge-transfer, etc.) in a series of solvated molecules (acrolein, indigo, p-nitro-aniline, donor–acceptor complexes, etc.) for which we compare BSE solvatochromic shifts to those obtained by linear-response and state-specific TD-DFT implementations. Such a remarkable and unique feature is particularly valuable for the study of solvent effects on excitations presenting a hybrid localised/charge-transfer character.

中文翻译：

具有可极化连续体嵌入的 Bethe-Salpeter 形式主义：协调线性响应和状态特定特征†

Bethe-Salpeter 方程 (BSE) 形式最近已被证明是时间相关密度泛函理论 (TD-DFT) 的一个有价值的替代方案，其计算时间随系统规模的变化而变化。特别是，TD-DFT 的有问题的转变（例如电荷转移、里德伯和花青样激发）已被证明可以用 BSE 准确描述。我们在这里证明，将 BSE 形式与可极化连续介质模型 (PCM) 相结合，使我们能够同时包含线性响应和状态特定对溶剂化显色的贡献。通过探索一系列溶剂化分子（丙烯醛、靛蓝、对硝基苯胺、供体-受体复合物等）中各种性质（局部、电荷转移等）的转变，我们可以比较 BSE 溶剂化变色性，从而证实了这一点。转向通过线性响应和特定于状态的 TD-DFT 实现获得的结果。这种显着而独特的特征对于研究溶剂对激发的影响（呈现混合局域/电荷转移特征）特别有价值。

更新日期：2018-04-05

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